Detergent motor fuel

ABSTRACT

Detergent motor fuel compositions are disclosed and claimed which are particularly useful in spark-ignition, internal combustion engines. The detergent compositions of the present invention contain certain additives which either substantially eliminate or maintain at a low level deposits which would otherwise form in the carburetor and in the intake valves and ports. Such carburetor and intake system deposits are to be avoided since they tend to restrict the flow of air through the carburetor especially at idle and at low speeds and/or cause improper valve closing and sluggish valve action. These conditions produce rough engine idling, stalling and can also result in excessive hydrocarbon and carbon monoxide exhaust emissions.

United States Patent [191 Machleder et al.

[ 1*Sept. 23, 1975 DETERGENT MOTOR FUEL [75] lnventors: Warren H. Machleder, Elkins Park;

Robert R. Kuhn, Lansdale, both of Pa.

[73] Assignee: Rohm & Haas Company,

Philadelphia, Pa.

21 Appl. No.: 398,621

Related U.S. Application Data [63] Continuation of Ser. No. 279,891, Aug. 11, 1972,

Pat. No. 3,782,912.

3,231,348 1/1966 Lindstrom et al. 44/72 3,399,982 9/1968 Kautsky 44/69 3,438,757 4/1969 Honnen et a1. 44/58 3,574,574 4/1971 Moore et a1. 44/66 3,782,912 l/1974 Machleder ct a1. 44/66 OTHER PUBLICATIONS Rohm and Haas Brochure tA1ky1 Amines.

Primary Primary ExaminerDelbert E. Gantz Assistant E.\'aminerAndrew H. Metz [57] I ABSTRACT Detergent motor fuel compositions are disclosed and claimed which are particularly useful in spark-ignition, internal combustion engines. The detergent compositions of the present invention contain certain additives which either substantially eliminate or maintain at a low level deposits which would otherwise form in the carburetor and in the intake valves and ports. Such carburetor and intake system deposits are to be avoided since they tend to restrict the flow of air through the carburetor especially at idle and at low speeds and/or cause improper valve closing and sluggish valve action. These conditions produce rough engine idling, stalling and can also result in excessive hydrocarbon and carbon monoxide exhaust emissions.

4 Claims, No Drawings DETERGENT MOTOR FUEL This is a continuation, of application Ser. No. 279,891, filed Aug. 11, 1972, now U.S. Pat. No. 3,782,912.

This invention relates to motor fuel compositions for spark ignition, internal combustion engines. More particularly, this invention relates to a detergent motor fuel containing additives which reduce or prevent the formation of deposits in the carburetor. Thus, for formulations of the present invention are particularly effective as carburetor detergents to clean up and maintain the cleanliness of the carburetor. Other additives may also be present to reduce or prevent deposits in the induction system such as the areas around the ports and valves. This invention also relates to the mixture or combination of additives.

Modern internal combustion engine design is undergoing and has undergone important changes to meet stricter standards for engine and exhaust gas emissions. A major change in engine design is the feeding or recycling of blow-by gases from the crankcase of the engine into the intake air supply to the carburetor rather than the venting of these gases to the atmosphere, as in the past. The blow-by gases contain substantial amounts of deposit-forming substances and are known to form deposits in and around the throttle plate area of the carburetor. These deposits restrict the flow of air through the carburetor at idle and at low speeds so that an overrich fuel mixture results. This condition produces rough engine idling, stalling and also results in excessive hydrocarbon and carbon monoxide exhaust emissions being emitted to the atmosphere.

In addition to the changes that have already been made, it is anticipated that additional burdens and demands will be placed on present day internal combustion engines and their fuels with the advent of new emission control devices, such as exhaust gas recirculation systems and exhaust catalytic mufflers. Also, the use of certain fuel additives such as the alkyl ammonium phosphate detergents may have to be restricted or eliminated because catalytic exhaust mufflers which utilize metal catalysts will be poisoned by phosphoruscontaining compounds.

it is an object of the present invention to provide a detergent motor fuel which will have certain carburetor detergent properties and which will clean up and maintain the cleanliness of the carburetor and optionally the remainder of the fuel induction system such as the valves and ports. It is another object of the present invention to provide a detergent fuel which will maintain a low level of hydrocarbon and carbon monoxide exhaust gas emissions and which will avoid the use of phosphorus-containing additives. It is still a further object of the present invention to provide a detergent fuel which has other desirable properties such as rust and corrosion protection, water demulsibility properties, anti-icing properties, etc. It is a further object of the present invention to provide multi-functiona] gasoline additives which are effective in inhibiting the formation of intake valve deposits in addition to being effective as carburetor detergents, and which can be used at relatively low concentrations (and thus at relatively low cost) for example at a treating level of about 1000 parts per million (ppm on a weight basis in the gasoline), or less, and more preferably 600 ppm or less, and even more preferably 400 ppm or less.

There are, l of course, other detergent motor fuel compositions available today, but they generally suffer from one or more deficiencies. Either they are used at very high concentrations, for example, something of the order of 4000 ppm; or if used at the use levels in which we are interested, the available formulations suffer from one or more defects.

We have discovered that the combination of (1) selected tertiary alkly primary amines having branched backbones and a total of about 6 to 24 carbon atoms, and more preferably, a total of 12 to 22 carbon atoms; (2) a surface active ammonium carboxylate saltethoxylated alkyl phenol ester of a trimer or dimer acid; and (3) a hydrocarbon-soluble polyisobutylene (or polybutene) having a number average molecular weight (Mfi) of from about 700 to about 3000 and a viscosity of from about 9000 to 900,000 sus at 100 F. and of from about 300 to 20,000 sus at 210 F., are effective in reducing or preventing the formation of carburetor and other induction system deposits.

According to the present invention, therefore, we provide a normally liquid, multi-functional additive composition for addition to a leaded, low lead, or unleaded gasoline, i.e., to a distillate hydrocarbon fuel comprising a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range. The three component composition ranging from a total of about 180 to about 1000 parts, on a weight basis, is comprised of about 20 to about 250 parts, and more preferably, about 50 to 100 parts by weight of l a tertiary alkyl branched chain primary amine, as above described; about 10 to about 100 parts and, more preferably, about 25 to about 50 parts by weight of (2) a surface active alkyl ammonium carboxylate saltethoxylated alkyl phenol ester of a trimer or dimer acid, as above described; and about 150 to about 650 parts by weight and, more preferably, about 200 to 400 parts by weight of (3) a hydrocarbon-soluble polybutene, as above described. In an alternative embodiment of the invention and where carburetor detergency and rust inhibition, per se, are primarily desired, then the polybutene component (3) can be omitted, and a two component additive composition can be utilized, which, on a total weight basis of about 30 to about 350 parts, is comprised of about 20 to 250 parts and, more preferably, 50 to 100 parts by weight (1) the tertiary alkyl branched chain primary amine, above-noted; and about 10 to about 100 parts and, more preferably, about 25 to 50 parts by weight of (2) the surface active salt-ester, above-noted. Thus, a preferred two component additive composition comprises about 50 to about 100 parts of l) and about 25 to 50 of (2) in a total of about parts to about 150 parts, all parts being on a weight basis.

On a treating level basis, i.e., on a level related to the gasoline, the three component additive composition should be added to or used in the gasoline at a total level of about 180 to about 1000 ppm (weight basis) and, on an individual or component basis, in an amount of from about 20 to 250 ppm, and more preferably 50 to ppm of (1 10 to 100 ppm, more preferably 25 to 50 ppm of (2); and to 650 ppm, more preferably 200 to 400 ppm of (3). On a pounds per barrel of gasoline basis this is 5 to 62.5, more preferably 12.5 to 25 lbs/1000 barrels(bbls.) of gasoline of (1); 2.5 to 25, more preferably 6.25 to 12.5 lbs/1000 bbls. of gasoline of (2); and 37.5 to 162.5, more preferably 50 to 100 lbs/1000 bbls. of gasoline of (3).

For the two component additive composition, the pounds per barrel of gasoline treating level is the same as noted for components (1) and (2) above.

The tertiary (tert.) or t-alkyl primary amine, having at least one branched chain, may be represented by the general formula (I) in which R R and R are alkyl groups whose total carbon atom content ranges from 6 to 24. It is preferred that two of the R groups, for example, the R and R of the t-alkyl primary amine be methyl groups.

The t-alkyl primary amines, having a branched chain, which may be used in the compositions of the present invention include, for example, t-octylamine, tnonylamine, t-dodecylamine, t-tetradecylamine, toctadecylamine, t-docosylamine, t-tetracosylamine and mixtures of two or more of such amines. These amines are commonly prepared by reactions known to those skilled in the art such as the reaction of nitriles with alkenes or secondary or tertiary alcohols in strongly acidic media. Commercially available t-alkyl primary amines are often mixtures. t-Octylamine having a branched structure has the formula and the aklyl group of this amine will hereinafter be referred to as t-octyl. One form of t-nonylamine is prepared as a mixture containing and has a neutral equivalent of about 142. A commercial preparation which is useful in the present invention is available under the trademark Primene 8l-R which is a mixture of t-dodecyl-, t-tridecyland ttetradecylamines or principally a mixture of t- C H NH to t-C H NH amines having a neutral equivalent of about 191. Another commercial preparation which is useful in the present invention is available under the trademark Primene JM-T which is principally a mixture of t-C, H -,NH to t-C H Nl-l and which has a neutral equivalent of about 315. The important consideration is that in a t-alkyl primary amine, the NH group is always attached to a carbon atom containing no hydrogen atoms and in the present invention at least one of the alkyl groups is branched.

The alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid which is added or included, primarily to provide rust and corrowhere n is an average number from 1.5 to 12.5 and more preferably from about 3 to 10; and in the case of a salt-ester derived from a trimer acid x is l or 2, and

y is l or 2, the sum ofx and y being 3;

and in the case of the salt-ester derived from a dimer acid, both 1: and y are each 1;

R is an alkyl group containing 4 to 12 carbon atoms;

R is H or an alkyl group containing 4 to 12 carbon atoms;

R is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amine substituted alkyl group of 2 to 24 carbon atoms. Preferably, R contains 12 to 22 carbon atoms; and

Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms.

The alkyl ammonium carboxylate salt-ester, i.e., component (2), may be used as all trimer acid derivative or all dimer acid derivative, or any mixture of the dimer and trimer acid derivatives may be used in the present invention.

Also, the presence of some monocarboxylic C acids or the like in the ester or salt form, or mixtures of both ester and salt form, may be tolerated in minor amounts, about 5% or less.

TABLE I Alkyl Ammonium Carboxylate Salt-Ester R polyisobutylene) as used herein is meant to include polymers which may have incorporated in the polymer chain minor amounts of l-butene and 2-butene units. The polyisobutenes are conveniently obtained by polymerizing isobutene or mixtures of isobutene with small amounts of l-butene and/or 2-butene, according to known methods. Polybutenes which may be used in this invention and commercially available. Further examples of and descriptive material relating to useful polybutenes may be found in British Pat. No. 1,258,549.

The molecular weights referred to hereinabove are number average molecular weights determined by vapor pressure ismometry according to ASTM D-2503. Thus the polybutene component of this invention having molecular weights in the range 700 to 3000 are mixtures of polybutene molecules averaging from about 12 to about 54 C H units in the polymer chain, with each molecule containing an olefinic double bond, analyzable by titration with bromine according to standard methods, such as ASTM D-1l59.

The molecular weight and molecular weight distribution among the polybutene molecules in'these mixtures are such that the viscosities of these normally liquid materials range from about 9000. SUS at 100F. and from about 300 SUS at 210F. for the low (700) molecular weight polymers to about 900,000 SUS at 100F. and about 20,000 SUS at 210F. for the high (3000) molecular weight polymers, the viscosities being determined according to ASTM D-445 and 446.

Preferred polybutenes useful in the present invention have molecular weights in therange of 950 to 1400 and viscosities in the range 1050 to 2990 SUS at 210F. and in the range of 40,000 to 123,000 SUS at 100F. Preferably, the polybutene is primarily (80% or more) polyisobutylene or polyisobutene. Mixtures of two or more of the various polybutenes may be used if desired.

The polybutenes are the preferred additive for induction system deposit (ISD) control. However, the polybutene may be replaced in whole or in part by mineral oil for [SD control; or the polybutene or mineral oil may be omitted entirely where ISD control is not considered necessary or where other additives may be used for [SD control.

The alkyl ammonium carboxylate salt ester can be made in known fashion, by the acid catalyzed esterification of a suitable trimer or dimer acid; for example, in the case of the diester-monosalt, with two moles of a suitable ethoxylated alkyl phenol followed by conversion of the remaining carboxylic acid function to an alkyl ammonium carboxylate salt with the addition of a suitable'amine. The trimer acid may be the product derived from the trimerization reaction of a C unsaturated fatty acid; an example of a suitable trimer acid is that available under the trademark Empol 1041. A generalized reaction scheme for the preparation of an alkyl ammonium carboxylate salt-ester is shown below.

1) Acid C51 (C02H)3 2H0 (CH CH O) --2-)--2H-O) Trimer Acid 5 n, R R and R have the values given previously, and C is the carbon atom content of the hydrocarbon residue.

in the following examples which illustrate this inven tion, all parts and percentages are by weight, unless otherwise stated. The ability of the additive combinations of this invention to clean up and maintain the cleanliness of the carburetor of an internal carburetor engine is illustrated by the carburetor detergency engine tests described below. The gasoline fuel for Tables I1 and 111 (an MS-OS gasoline) has the following properties.

Gravity 59.7

API Sp. Gr. at 60F. ASTM D-86 Distillation, F.

18? 93 10% 123 50% 205 348 E. P. 405 7: Recovered 98 7( Residue l Loss 1 Sulfur 0.1 1 Lead, Gm/gal 3.08 FlA Composition Aromatics, 71 23.1 Olefins, 7r 20.0 Saturates, 7: 56.9 Oxidation Stability, Minutes 600+ ASTM Gum (unwashed), mg/IOO ml 1.0 Research Octane Number 95.5 7: H 13.10 7: C 86.61 H/C 1.80

ENGINE TEST EVALUATION OF MULTIPURPOSE CARBURETOR DETERGENTS A. Blowby Carburetor Detergency Keep Clean Engine Test 1. Engine Test Procedure The Blowby Carburetor Detergency Keep Clean Engine Test (BBCDT-Keep Clean) measures the ability of a gasoline additive to keep clean the carburetor throttle body area, and is run in a 1970 Ford 351 CID V-8 engine equipped by means of a special Y intake manifold with two one-barrel carburetors, which can be independently adjustedand activated. With this arrangement, a separate test fuel can be evaluated by each carburetor which feeds four of the eight cylinders via the non-interconnected"intake manifold. The carburetors are modified with removable aluminum sleeves in order to facilitate weighing of the deposits which accumulate in the throttle body area. The severity of the test is adjusted to an appropriate level by recycling the entire amount of blowby gases, approximately 90l 10 CFH, to the top of the air cleaner so that each carburetor receives an equal volume of these gases. Equal intake mixture flow through each carburetor is adjusted dur ing the first hour ofoperation of means of intake manifold differential pressure and CO exhaust gas analysis. The following test cycle and operating conditions are employed:

Test Cycle:

Phase I 650 engine rpm, 8 min. Phase 11 3000 engine rpm, 1 min.

, Test Duration, hrs. 10

Control Untreated 15.9

Gasoline l l/ll* 50/25 2.3

4 l/ll/lll 50/25/44() 2.6

*Additive component l is a tert. C C alkyl amine with a highly branched backbone. a molecular weight principally in the l85-2l3 range, and a neutral equivalent of 191; additive component ll is essentially an alkyl ammonium carboxylate salt-ester of formula III:

Z (III) where Z is the hydrocarbon residue of the product of trimerization of an unsaturated C fatty acid, the trimer acid as for example beingEmpol 1041 (Emery lndustries lnc.). It is understood that Empol 1041 is a mixture of about 90% trimer acid (C and about 10% dimer acid (C Additive component Ill is a hydrocarbon-soluble polyisobutylene having a number average molecular weight (MTT) of about l000; additive component IV is a tert. C -C alkyl aminewith a highly branched backbone, a molecular weight principally in the 269-325 range and a neutral equivalent of 315.

it is apparent from Table ll that the additive combination or mixture of Example l, which contains parts of component I in admixture with 25 parts of compo nent II, is an effective carburetor detergent, as is the combination or mixture of Example 4. The effectiveness of the carburetor detergency is shown by the weight of the deposits, the less the deposit weight, the more effective the carburetor detergent. Thus, the untreated MS-O8 gasoline gave a deposit weight of 15.9 mg. in the keep clean test, whereas the combination of Example I gave only 2.3 mg., andthe combination of Example 4 gave only a 2.6 mg. weight deposit, both of which are significantly lower than the untreated gasoline. It is also apparent from Table II that component II has carburetor detergent properties, in addition to its rust inhibition properties, as shown hereinaften B. Blowby Carburetor Detergency Clean Up Engine Test The Blowby Carburetor Detergency Clean Up En- Continued that of the BBCDT-heep Clean procedure except that lntake Air, C. 135 i 10 I the carburetor alum num sleeves are dirtied up first by .llzacket \gfit sr. C- F f running untreated M8 08 gasoline, then cleaned up by n "10 lum g in Exhaust 30 i 02 runn ngadditive treated gasoline. Test results are re- Blo y. CFH 0- 5 corded as weight (mgs) of deposits accumulated and removed from the sleeves, and reported as percent The weight (mgs.) of deposits accumulated on the l an u aluminum sleeve is measured, and the average value of TABLE In four tests per additive or additive mixture is reported.

10 Blowby Carburetor Detergency Engine Test -TABLE ii Clean Up I Additive Treating Percent Clean Up Example Com- Level, ppm (avg. of 4 tests) Blowby Carburetor Detergency ponent(s) Engine Test Keep Clean l5 6 l/ll* 50/25 19.5 Treated Level, Deposit Wgt. mg 7 I 50 l6.3 Example Additive ppm (in gasoline) (avg. of4 tests) 8 l/ll/m 50/25/300 19,6 I 9 IV 50 23.9

*Additive components, I, ll, Ill and lV are the same as given previously. In the clean up" test. the higher the percentage clean up, the more effective the additive combinations or mixtures. Thus. it is apparent from Table III that Examples 6 and 8 produce significant clean up. The untreated MS-08 gasoline, i.e.. without the additives, gave a value of minus 22.3% clean up. i.c., additional dirtying of 22.37:.

C. Slave Engine Carburetor Detergency Engine Test The Slave Engine Carburetor Detergency Engine Test (SECDT) is similar to the BBCDT except that the severity is adjusted to an appropriate level by feeding a portion of the exhaust gases from Labeco slave engine' into the top of the air cleaner of the Ford carburetor detergency engine. This is intended to simulate the use of exhaust gas recirculation (EGR) systems such as those being developed by the automotive industry to help control exhaust pollutants.

Additive components I and ll are the same as given previously. The gasoline used in the test reported in Table IV is unleaded gasoline having the following properties.

Research Octane No. (RON) 9l.2-9l.0 Distillation, F.

lBP 88-90 10% l26-l 30 5071 214-224 9071 343-347 E.P. 385-414 FlA 72 Aromatics 23.9-25.9 7! Oleflns l8.7-l5.8 7: Saturates 57.4-58.3 Sulfur Natural Wt. 71 0.088-0084 Gum (washed) mg. 0.8 Lead, ppm 0.8-1.8

An inspection of Table IV shows that the combination or admixture of components I and II give the lowest mg. deposit in this keep clean test.

D. Induction System Deposit Engine Test 1. Engine Test Procedure The Induction System Deposit Test (ISDT) which is used to evaluate the ability of gasoline additives or mixtures of additives to control induction system deposits,

TABLE V Induction System Deposit Engine Test Treating Level (Valve and Port) Example Additive ppm (in gasoline) Deposits, mg

13 Untreated 475 gasoline 14 U" 250/25 977 15 l/ll/lll* 250/25/300 446 Additive components I, ll and 11] same as given before.

The untreated gasoline was the same as used for the test reported in Table IV. Example 15, comprising the combination of components l, 11 and 111 exhibits improved induction system deposit control. keeping in mind that components 1 and II need be added for carburetor detergency and rust inhibition performance.

TABLE VI Rust Inhibition Test (ASTMD-665) Example Addditive Treating Level, ppm 7: Area Rusted 16 Isooctane 80 (control) 17 U" 250/20 1 18 l 250 65 19 ll 20 2 Additive components I and 11 are the same as identified previously.

The above Table VI shows that the combination of l and 11 gives good rust inhibition and exhibits a very marked improvement over the component (I), i.e., only 1% area rusted vs. 65% area rusted in the aboveidentified ASTM test.

As noted previously, the polyisobutylene (or polybutene) component may be'omitted entirely (where induction system deposit control is not deemed necessary) or it may be replaced in whole or part with mineral oil to control induction system deposits. Where mineral oil is used, however, it generally has to be used at a higher treating level for lSD control, for example at a level of about 2 to times as high as the polybutene component.

Other additives may be included in or within the two or three component additive composition of the present invention. Also, it is sometimes desirable to include a minor amount of an alcohol such as n-butanol, for example, about 5-15 weight percent, with the three component additive composition to form a non-separating solution of the three component package to improve handling characteristics.

While the above disclosure refers to component (2) as an ethoxylated ester, it will be understood that the equivalent propoxylated analogues may also be used. Also, in the claims where reference is made to the alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid, it will be understood 10 that mixtures of such trimer and dimer acid salt-esters are also embraced and-included.

We claim: a 1

1. A multi-functional additive composition suitable for addition to distillate hydrocarbon fuels having a major proportion of a hydrocarbon base fuel distilling within the gasoline distillation range, the additive composition comprising a mixture of 1. about 20 to 250 parts by weight of a tertiary alkyl primary amine having a branched bacckbone and wherein backbone tertiary alkyl primary amine has a total carbon atom content of 18 to 22 carbon atoms;

2. about 10 to parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid;

3. about to 650 parts by weight of a hydrocarbonsoluble polybutene having a number-average molecular weight (Mn) of from about 700 to about 3000.

2. A detergent additive composition suitable for addition to gasoline comprising a mixture of 1. about 20 to 250 parts by weight of a tertiary alkyl primary amine and wherein said tertiary alkyl primary amine has a total carbon atom content of about 18 to 22 carbon atoms;

2. about 10 to about 100 parts by weight of a surface active alkyl ammonium carboxylate saltethoxylated alkyl phenol ester of a trimer or dimer acid of the formula [c0 ma a j where n is an average number from 1.5 to 12.5; in the case of a salt ester derived from a trimer acid x is 1 or 2, and

y is 1 or 2, the sum of x and y being 3;

and in the case of the salt ester derived from a dimer acid, both x and y are each 1;

R, is an alkyl group containing 4 to 12 carbon atoms;

R, is H or an alkyl group containing 4 to 12 carbon atoms;

R, is an alkyl group containing 2 to 24 carbon atoms which may be straight or branched chain or an amine substituted alkyl group of 2 to 24 carbon atoms; and

Z is a saturated or unsaturated hydrocarbon residue of the acid, said hydrocarbon residue having 34 to 51 carbon atoms.

3. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (B) about to 1000 ppm of the additive composition comprising (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a total carbon atom content of 12 to 14 carbon atoms, and (2) about 10 to about 100 parts by weight of a surface active alkyl ammonium carboxylate salt ester of the formula 6 C 2 N ia 12-1u 25-29 lecular. weight (M'rT) of from about 700 to about I 3,000. 4. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (B) about 30 to 350 ppm of the additive 1 2 composition comprising l about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a total carbon atom content of 12 to 14 carbon atoms,-

and (2) about to-about 100 parts by weight of a sur- 5 face active alkyl ammonium carboxylate salt ester of the formula 15 where Z is the hydrocarbon residue of the product of trimerization of an unsaturated C fatty acid.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent o- 1907518 Dated September 25, 1975 lnventor(s) Warren H. Maohleder; et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 10, "baookbone' should read backbone line 11, "backbone" should read said Signed and Scaled this twenty-seventh D f January 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Attesting Officer Commissioner ofPatents and Trademarks 

1. A MULTI-FUNCTIONAL ADDITIVE COMPOSITION SUITABLE FOR ADDITION TO DISTILLATE HYDROCARBON FUELS HAVING A MAJOR PROPORTIONS OF A HYDROCARBON BASE FUEL DISTILLING WITHIN THE GASOLINE DISTILLATION RANGE THE ADITIVE COMPOSITIVE COMPRISING A MIXTURE OF
 1. ABOUT 20 TO 250 PARTS BY WEIGHT OF A TERTIARY ALKYL PRIMARY AMINE HAVING A BRANCHED BACKBONE AND WHEREIN BACKBONE TERTIARY ALKYL PRIMARY AMINE HAS A TOTAL CARBON ATOM CONTENT OF 18 TO 22 CARBON ATOMS,
 2. ABOUT 10 TO 100 PARTS BY WEIGHT OF A SURFACE ACTIVE ALKYL AMMONIUM CARBOXYLATE SALT-ETHOXYLATED ALKYL PHENOL ESTER OF A TRIMER OR DIMER ACID,
 2. about 10 to 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid;
 2. A detergent additive composition suitable for addition to gasoline comprising a mixture of
 2. about 10 to about 100 parts by weight of a surface active alkyl ammonium carboxylate salt-ethoxylated alkyl phenol ester of a trimer or dimer acid of the formula
 3. about 150 to 650 parts by weight of a hydrocarbonsoluble polybutene having a number average molecular weight (Mn) of from about 700 to about
 3000. 3. ABOUT 150 TO 60 PARTS OBY WEIGHT OF A HYDROCARBONSOLUBLE POLYBUTENE HVING A NUMBER AVERAGE MOLECULAR WEIGHT (MN) OF FROM ABOUT 700 TO ABOUT
 3000. 3. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (B) about 180 to 1000 ppm of the additive composition comprising (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a total carbon atom content of 12 to 14 carbon atoms, and (2) about 10 to about 100 parts by weight of a surface active alkyl ammonium carboxylate salt ester of the formula
 4. An improved detergent motor fuel composition comprising (A) a major proportion of a hydrocarbon base fuel boiling in the gasoline boiling or distillation range and (B) about 30 to 350 ppm of the additive composition comprising (1) about 20 to about 250 parts by weight of a tertiary alkyl primary amine having a total carbon atom content of 12 to 14 carbon atoms, and (2) about 10 to about 100 parts by weight of a surface active alkyl ammonium carboxylate salt ester of the formula 